Spectroscopic and computational studies of a series of high-spin Ni(II) thiolate complexes.
Spectroscopic and computational studies of a series of high-spin Ni(II) thiolate complexes.
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一系列高自旋 Ni(II) 硫醇络合物的光谱和计算研究。
DOI：
10.1021/ic100362q
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发表时间：
2010
影响因子：
4.6
通讯作者：
Brunold,ThomasC
中科院分区：
文献类型：
--
作者：
VanHeuvelen,KatherineM;Cho,Jaeheung;Dingee,Timothy;Riordan,CharlesG;Brunold,ThomasC
采用光谱和计算相结合的方法，研究了一系列高自旋镍硫醇盐配合物[PhTttBu]Ni（SR）（R = CPh 3，2; C6 F5，3; C6 H5，4; PhTttBu=苯基三（（叔丁基硫代）甲基）硼酸酯）的电子结构.共振拉曼（rR）光谱数据表明，这些物种的νNi− SR振动特征发生在404和436 cm− 1之间。由于涉及能量接近的电子激发态的干扰效应，相应的RR激发曲线显示出显著的去增强行为。这些数据进行了分析，在含时海勒理论的框架内获得定量的洞察激发态核扭曲。2 − 4的电子吸收光谱和磁性圆二色性光谱的特征是大量的电荷转移（CT）跃迁。在所有三种复合物中，主要的吸收特征发生在18,000 cm− 1处，被认为是硫醇盐到Ni的CT跃迁，涉及相对于Ni−S键具有π对称性的分子轨道，这让人想起蓝铜蛋白质的特征吸收特征。密度泛函理论的计算数据提供了2 − 4的分子轨道描述，并允许对关键的光谱特征进行详细的分配。在这项研究中获得的结果与那些报道的类似镍硫醇盐物种的比较表明，支持配体在确定光谱特性方面起着次要作用，因为电子结构主要由金属-硫醇盐键合相互作用决定。
The electronic structures of a series of high-spin Ni(II)-thiolate complexes of the form [PhTttBu]Ni(SR) (R = CPh3,2; C6F5,3; C6H5,4; PhTttBu= phenyltris((tert-butylthio)methyl)borate) have been characterized using a combined spectroscopic and computational approach. Resonance Raman (rR) spectroscopic data reveal that the νNi−SRvibrational feature occurs between 404 and 436 cm−1in these species. The corresponding rR excitation profiles display a striking de-enhancement behavior because of interference effects involving energetically proximate electronic excited states. These data were analyzed in the framework of time-dependent Heller theory to obtain quantitative insight into excited state nuclear distortions. The electronic absorption and magnetic circular dichroism spectra of2−4are characterized by numerous charge transfer (CT) transitions. The dominant absorption feature, which occurs at ∼18,000 cm−1in all three complexes, is assigned as a thiolate-to-Ni CT transition involving molecular orbitals that are of π-symmetry with respect to the Ni−S bond, reminiscent of the characteristic absorption feature of blue copper proteins. Density functional theory computational data provide molecular orbital descriptions for2−4and allow for detailed assignments of the key spectral features. A comparison of the results obtained in this study to those reported for similar Ni-thiolate species reveals that the supporting ligand plays a secondary role in determining the spectroscopic properties, as the electronic structure is primarily determined by the metal−thiolate bonding interaction.
影响因子：
64.8
作者：
FRANCHINI, G;GURGO, C;REITZ, MS
通讯作者：
REITZ, MS
CD8 淋巴细胞抑制猴免疫缺陷病毒体外复制。
DOI：
--
发表时间：
1988
期刊：
Journal of immunology (Baltimore, Md. : 1950)
影响因子：
--
作者：
Kannagi,M;Chalifoux,LV;Lord,CI;Letvin,NL
通讯作者：
Letvin,NL